EP3514206A1 - Thermoplastique - Google Patents

Thermoplastique Download PDF

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Publication number
EP3514206A1
EP3514206A1 EP18152573.4A EP18152573A EP3514206A1 EP 3514206 A1 EP3514206 A1 EP 3514206A1 EP 18152573 A EP18152573 A EP 18152573A EP 3514206 A1 EP3514206 A1 EP 3514206A1
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EP
European Patent Office
Prior art keywords
polyester
powder coating
mol
coating composition
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18152573.4A
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German (de)
English (en)
Inventor
Ingrid HINTERSTEINER
Sabrina Weigl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tiger Coatings GmbH and Co KG
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Tiger Coatings GmbH and Co KG
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Filing date
Publication date
Application filed by Tiger Coatings GmbH and Co KG filed Critical Tiger Coatings GmbH and Co KG
Priority to EP18152573.4A priority Critical patent/EP3514206A1/fr
Priority to CN201980009299.8A priority patent/CN111630115B/zh
Priority to PCT/EP2019/051220 priority patent/WO2019141800A1/fr
Priority to EP19700609.1A priority patent/EP3740539B1/fr
Publication of EP3514206A1 publication Critical patent/EP3514206A1/fr
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/20Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6858Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6888Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6928Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints

Definitions

  • the present invention relates to a thermoplastic, unsaturated semi-crystalline polyester (A) with a Mp of 35°C or above comprising allyl functional groups, a process for the production of such a polyester (A), use of such a polyester (A) in a binder system of a powder coating composition and a powder coating composition comprising at least one thermoplastic polyester (A) and at least one thermoplastic amorphous polymer (B) comprising ethylenic unsaturations, wherein polyester (A) and polymer (B) can copolymerize with each other.
  • powder coatings are a very environmentally friendly kind of a coating material.
  • the nearly complete degree of material utilization, the freedom from VOC content, and its simple application are leading to an increase in the market share of powder coatings.
  • the relatively high baking temperature of typically between 150 and 200°C the coating of heat-sensitive substrates with powder coatings presents a technological challenge.
  • hybrid powder coatings have usually been employed for the coating of heat-sensitive substrates which are characterized by low baking temperatures and a markedly improved UV resistance compared to epoxy resin powder coatings.
  • the lowest curing temperatures that can be achieved with such systems are around 130 °C because lower curing temperatures would lead to insufficient storage stability caused by high concentrations of curing catalysts.
  • radically curing systems have been employed both currently and in the past.
  • crystalline or partially crystalline resins are recommended in the state of the art, in particular because a homogeneous mixing of such resins with amorphous resins turns out to be difficult due to clearly varying melt viscosities.
  • the edge coverage may turn out to be insufficient if a too high concentration of crystalline resin(s) is used.
  • EP 0 309 088 B1 describes a powder composition for an in-mold process, including at least one unsaturated polyester and at least one copolymerizable second resin, as well as an amount of an initiator sufficient to crosslink the mixture which in turn consists of a mixture of a rapid and a slow initiator.
  • EP 1 043 138 A1 relates to thermosetting resins for use as a surface coating of glass fiber reinforced molded articles in the mold wherein the resins are in powder form.
  • the systems described in these two disclosures are aimed at making use of the powderin-mold-coating (PIMC) process.
  • the powder is applied to the surface of the mold preferably when the surface of the mold is sufficiently hot to cause melting of the powder particles and to partially cure the film resulting from this.
  • the mold coated like this is filled with a fluid, thermally curing filling resin with or without a glass fiber reinforcement.
  • the combined curing of the coating and the filling resin is effected under applied pressure (in a press).
  • applied pressure in a press.
  • lower curing temperatures can be reached hereby, compared to conventional powder coating systems, these are still in a temperature range with lower curing temperatures of about 150°C which is clearly too high for heat-sensitive substrates.
  • flowing and leveling i.e. the melting viscosity, does not play a role in PIMC, resulting in far higher coating thicknesses.
  • a pressure is applied which is not the case in powder coatings and is even undesirable.
  • US 3 331 891 describes a composition in powder form, comprising allyl prepolymers and unsaturated polyesters, with thermal curing.
  • the number average molar mass of the allyl prepolymer is maximally 25,000 g/mol, and per 100 parts of the allyl prepolymer, and there will be included 5 to 50 parts of an unsaturated polyester having a melting point of between 35 and 120°C, and a maximum of 10 parts of a diallyl phthalate monomer.
  • the composition includes a polymerization catalyst. Despite this polymerization catalyst, curing temperatures ranging from 150-160°C are still required for this composition in order to achieve an adequate crosslinking of this system.
  • compositions disclosed in this document do not enable the coating of temperature-sensitive substrates, and the high baking temperatures for the coatings stated in the examples result in particular from the high proportion of diallyl phthalate prepolymer of at least two third based on the binding agent and from the high viscosity in the system caused by this. Further, the employed polyester is not focussed on viscosity lowering, semi-crystalline resins, and therefore no viscosity reduction can be achieved even with the addition of this component.
  • EP 0 844 286 A1 refers to a powder coating composition having a dual curing mechanism, comprising a resin with reactive unsaturated groups, such as unsaturated polyesters, unsaturated polyacrylates, unsaturated polymethacrylates, or mixtures thereof, a copolymerizable second resin having either a vinylester group, an acrylate group, a methacrylate group, an allylester group, or mixtures thereof, together with a photoinitiator and a thermal initiator.
  • EP 0 980 901 A2 and EP 1 538 186 A1 both describe radically curing systems with UV initiation. Both systems might not appropriate for three-dimensional substrate geometries; in such cases, a thermal iniation system might be preferred
  • EP 0 957 141 B1 describes a 2K system containing in the first component an unsaturated polyester and a free radical initiator and in the second component a polymerization accelerator.
  • a 2K system with a vinylether urethane crosslinker for curing the properties of the system described in EP 0 957 141 B1 which is based on allyl prepolymers, are described as being inadequate with respect to storage stability, extrudability, and swelling capacity.
  • CN 102884132 A and EP 2 566 923 A1 describe a heat curable powder coating composition, comprising at least one crystalline polyester resin and at least one amorphous polyester resin, at least one curing agent and at least one thermal radical starter, wherein the at least one crystalline polyester resin and/or the at least one amorphous polyester resin have/has diacid ethylenical unsaturations, the at least one curing agent is either crystalline or amorphous, and the at least one curing agent has reactive unsaturations, which can be crosslinked with the ethylenic double bonds of the diacid ethylenical unsaturations of the at least one crystalline polyester resin and/or the at least one amorphous polyester resin.
  • the curing agent is molecular or oligomeric (low molar mass) it may migrate to the surface during film formation or storage, and consequently during its usage as well.
  • this effect of "blooming" of low molecular compounds could be shown for powder coating compositions, and besides, this effect constitutes a problem known in the prior art.
  • coating compositions for heat sensitive substrates should have a very low viscosity at low curing temperatures on the one hand, enabling a good flow, meaning a smooth surface appearance, and levelling.
  • the storage stability of such coating compositions must not suffer.
  • the curing reaction must take place very fast, already at low temperatures, which means that conventional curing mechanisms such as a polyaddition and a polycondensation cannot be used, as they would require too high amounts of catalyst, which would in turn lead to chemical pre-reactions during storage.
  • Allylic polyesters are known from UV curing to give superior coating properties; however, only amorphous polyesters containing allylic functionalities have so far been described.
  • the shown carbon chain R carries on the one hand a number of m allyl groups, optionally via a connecting -X-, and is on the other hand connected via up to n groups - X- into one or more polyester chains of the backbone.
  • the respective definitions of R, X, n, m and p are given above.
  • the compounds supporting crystallinity are selected from the group comprising saturated and unsaturated, unbranched aliphatic, cycloaliphatic and aromatic alcohols, polyols, carboxylic acids, di- and polycarboxylic acids, anhydrides and derivatives thereof and compounds exhibiting more than one of the listed functional groups, wherein of cycloaliphatic and aromatic compounds the functional groups are preferably located opposite to each other for example in case of six-membered rings in para/1,4- position and in all cases the compounds supporting crystallinity contain no further substitution besides the above mentioned alcohol, anhydride or carboxylic groups or derivatives thereof.
  • polyester composition comprising lower amounts of aromatic compound supporting crystallinity often resulted in superior coating properties.
  • the polyester (A) according to the present invention has a peak maximum of melt temperature measured by differential scanning calorimetry of between 70 °C and 130 °C, more preferably between 80 °C and 120 °C, most preferable between 90 °C and 110 °C determined via DSC.
  • the polyester (A) according to the present invention has a melt enthalpy measured via DSC of more than 30 J/g, preferably more than 40 J/g.
  • the polyester (A) according to the present invention has a mass average molecular mass Mw between 2000 and 25000 g/mol, preferably between 4000 and 20000 g/mol.
  • the present invention is directed to a process for the production of a polyester (A), wherein suitably substituted allyl functional compounds are incorporated in a polyester-backbone, leading to a structure according to formula 1, for instance via alcohol, esters, anhydride or acid substituents.
  • the polyester (A) according to the present invention is used in a binder system of a powder coating composition, even more preferably in a powder coating composition comprising at least one of such thermoplastic semi-crystalline polyester (A) and at least one thermoplastic amorphous polymer (B) comprising ethylenic unsaturations, wherein polymer (B) has a Tg of between 30 °C and 75 °C, and wherein the components of the composition soluble in organic solvents have a weight average molecular mass of between 2,000 g/mol and 20,000 g/mol, and wherein polyester (A) and polymer (B) are capable of copolymerzing with each other.
  • polyester (A) enables a powder coating system which can be cured at very low baking temperatures.
  • temperature-sensitive substrates such as materials based on wood or plastics may be coated with a powder coating formulation containing polyester (A) of the invention at low baking temperatures and short baking times.
  • a powder coating formulation yields an optimum with respect to reactivity, in order to be able to coat heat-sensitive substrates and to achieve sufficient flowing/leveling of the coating, as well as to stability which is necessary for processing and storing the powder coating. This is realized by curing two binder components of very diverse properties which are copolymerizable with each other.
  • viscosity-lowering semi-crystalline allyl-functional polyester (A) combined with the second amorphous unsaturated polymer (B)
  • a highly reactive coating with low curing times, already at low curing temperatures, and a good storage stability, good smoothness of the coatings, good film properties (resistance against cold liquids, flexibility of the coating) can be achieved.
  • polymer (B) also high Tgpolymers (with Tg's up to 75 °C) can be used, such polymers normally cause poor surface appearance and processing problems.
  • the weight per unsaturation (WPU) of polymer (B) is between 140 and 2,000 g/mol, more preferably between 200 and 1200 g/mol, most preferably between 300 and 800 g/mol.
  • the WPU (weight per unsaturation) of polyester (A) is between 250 g/mol and 2000, preferably between 400 and 1500, most preferably 400 and 800.
  • Another preferred embodiment of the powder coating formulation of the invention includes a thermal and/or UV initiation system, in which in case of the thermal initiation the temperature, at which the half-life of at least one thermal initiator is one minute (in the following called T 1/2 ), is from 80 to 150°C, preferably from 90 to 140°C, particularly preferably from 100 to 130°C.
  • T 1/2 the temperature, at which the half-life of at least one thermal initiator is one minute
  • the thermal initiation system addtionally contains an accelerator to lower the T 1/2 , and/or an inhibitor to prevent a too early decomposition of the initiator and also too early cross-linking reactions of the binder. This means that thermal curing of the coating on heat-sensitive substrates is made possible by carefully selecting the components of the thermal initiation system, specifically with reference to the half life temperatures of the initiator and an optional addition of inhibitors and/or accelerators preventing a premature or too late initiator decomposition.
  • thermal iniators examples include azo initiators or peroxides, such as benzoyl peroxide, azobis (alkyl nitrile) peroxy compounds, peroxy ketals, such as 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, peroxy esters, dialkylperoxides, hydroperoxides, ketone peroxides, etc.
  • azo initiators or peroxides such as benzoyl peroxide, azobis (alkyl nitrile) peroxy compounds, peroxy ketals, such as 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, peroxy esters, dialkylperoxides, hydroperoxides, ketone peroxides, etc.
  • the powder coating formulation of the invention is characterized in that the thermal initiator includes a peroxide, preferably a dialkyl peroxide, a diacyl peroxide or a perester. Basically, other thermal initiators are possible as well. It is essential for the selection of the thermal initiator that the T 1/2 of the thermal initiator, which may optionally be adjusted by adding accelerators or inhibitors, is in a temperature range similar to the temperature at which the binder can be cross-linked.
  • the dosage of the peroxide is also of relevance. Excessively low peroxide doses may lead to insufficient cross-linking of the binder components, which in turn results in a poor swelling capacity and a deficient resistance to cold liquids. Excessively high peroxide concentrations, on the other hand, may result in pre-reactions during processing, storage problems, and odorous degradation products which may cause blooming.
  • the required concentration of the peroxide depends on the chemical structure of the peroxide as well as on the presence of fillers or phlegmatizing agents. If employed, the amount of thermal initiator present usually ranges between about 0.1 and about 10 %, and preferably between about 1 and 5 %.
  • the powder coating composition according to the present invention comprises besides or instead of the above-mentioned thermal initiator also a photoinitiator, preferably an UV initiator.
  • a photoinitiator preferably an UV initiator.
  • Such initiators are compounds being capable of initiating a polymerization/crosslinking reaction via a generation of active species when exposed to radiation (such as UV or IR).
  • aryl ketones for instance aryl ketones, acyl phosphine oxides, or azo initiators.
  • Fluther photoinitiators are for instance alpha cleavage photoinitiators including benzoin, benzoin ethers, benzyl ketals, such as benzyl dimethyl ketal, acyl phosphines, such as diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, aryl ketones, such as 1-hydroxy cyclohexyl phenyl ketone, Michler's ketone, diaryliodonium salts and copper synergists, etc.
  • the amount of photoinitiator present ranges between about 0.1 and 10 %, and preferably between about 1 and 5 %.
  • thermal initiators such as organic peroxide and azo compounds
  • organic peroxide and azo compounds in conjunction with the photoinitiators can also be employed.
  • thermal initiators alongside photoinitiators has been found to assist in curing down near the substrate, particularly when pigmented, opaque, or thicker film coatings are desired.
  • the powder coating composition might even not contain any initiator, especially if electron beam curing is used.
  • a powder coating composition containing the polyester (A) according to the present invention if the amount of the amorphous polymer (B) is between 20-90 % by weight, preferably between 40-75 % by weight, of the sum of (A) and (B).
  • the amount of the amorphous polymer (B) is between 20-90 % by weight, preferably between 40-75 % by weight, of the sum of (A) and (B).
  • the at least one thermoplastic amorphous polymer (B) does not contain or at least only low concentrations of allyl functionalities.
  • the powder coating composition of the present invention was found to be superior if the allyl group of polyester (A) does not react with an allyl group of the thermoplastic amorphous polymer (B) comprising ethylenic unsaturations.
  • the at least one thermoplastic, unsaturated semi-crystalline polyester (A) is understood to be a polyester according to claim 1 below including allyl groups which may subsequently undergo chemical reactions.
  • the production of the polyester may be achieved by adequate processes, such as polycondensation of bi- or multifunctional organic acids and/or anhydrides, and bi- or multi-functional alcohols, or by transesterification of, for example, methyl esters of the bi- or multifunctional organic acids.
  • the allyl compounds included into the synthesis must exhibit functional groups allowing an introduction into the polyester backbone, either directly during the synthesis of the polyester or via a subsequent modification of the polyester backbone.
  • Functional groups allowing an introduction into the polyester backbone either during the synthesis or via a subsequent modification of an existing polyester backbone as known to someone skilled in the art, such as alcohol and/or acid functionalities and/or derivatives thereof.
  • Substituted means within this invention that at least one H-atom is replaced by another atom or chemical group commonly known as substituent(s).
  • compound as used in the present invention is used for a building block with functional groups allowing the introduction into a polyester chain, said compound might be a monomer, oligomer or polymer.
  • polyester backbone as used within this invention describes the main chain of a polymer containing ester-functionalities (-[-CO-O-]-).
  • incorporated into a polyester backbone within the present invention means that the compound being included into the polyester chain can either bei located at the ends or within the polymer chain via any suitable functionalities.
  • the viscosity of the unsaturated semi-crystalline polyester (A) was done with an Inula Cap 2000+ Viscometer at 130 °C, using spindle 6, 700 rpm, and and measurement time of 115 s.
  • the number average molar mass is determined by gel permeation chromatography.
  • chloroform was used at a flow rate of 1 ml/min.
  • Calibration of the separation columns three columns of 8 mm x 300 mm each, PSS SDV, 5 ⁇ m, 100, 1000 and 100000 A was done by narrowly distributed polystyrene standards, and detection via refractive index detector.
  • Polymer (B) can be produced by radical polymerization, ionic polymerization, polyaddition, polycondensation or ring-opening polymerization or the like. It may be achieved in a way known to someone skilled in the art by polymerization of monomers containing ethylenic unsaturations and/or by chemical functionalization of polymers with compounds containing ethylenic unsaturations. Within the context of the present invention, the terms crystalline and semi-crystalline polyester are used synonymously, as there are no polymers with a 100% degree of crystallization. Unsaturated sites in the polymers may be achieved by using appropriate monomers, such as unsaturated alcohols or acids or derivatives thereof.
  • monomers favoring crystallizaton are particularly suitable, such as symmetrical compounds or compounds favoring the formation of hydrogen bridge bonds.
  • symmetrical compounds are those having at least one symmetrical axis.
  • compounds supporting a linear structure of the polymer with a very low tendency to form side chains are employed, for example linear unbranched bi-functional alcohols, acids or derivates thereof, having the functional groups opposite to each other.
  • the polymers may also include aromatic or cycloaliphatic monomers.
  • polyester (A) examples include terephthalic acid, isophthalic acid, ortho-phthalic acid, hexahydroterephthalic acid, tetrahydroterephthalic acid, benzoic acid, para-tert-butylbenzoic acid, cinnamic acid, crotonic acid, endomethylene tetrahydrophthalic acid, tetrachlorophthalic acid, 2,6-naphthalene dicarboxylic acid, 3,6-dichlorophthalic acid, cyclohexane dicarboxylic acid, adipic acid, succinic acid, nonanoic diacid, decanoic diacid, trimellitic acid, trimellitic acid anhydride, 4,4'-oxybis(benzoic acid), fumaric acid, maleic acid, maleic acid anhydride, itaconic acid, citraconic acid, mesaconic acid, neopentyl glycol,
  • the at least one thermoplastic amorphous polymer (B) comprising ethylenic unsaturations can be produced by processes known to the person skilled in the art using appropriate unsaturated monomers.
  • both the melting point and the melting enthalpy of the polymers were determined by DSC measurements based on ISO 11357-3. The measurement was done using a heating rate of 20 K/min.
  • the values stated in this invention for melting point and melting enthalpy refer to the Peak Melting Temperature and the Enthalpy of Melting stated in the standard.
  • T cure the same heating rate and the same temperature range are used. T cure is determined in the same way as the Peak Melting Temperature, but instead of the endothermic peak of melting the exothermic cross-linking peak is made use of.
  • the melting enthalpy and the peak melting temperature may be mainly influenced by the pre-treatment, processing or, in other words, thermal history of the polymer
  • the first heating run of the DSC is used for a first assessment of the peak melting temperature.
  • the polymer has to be cooled down to a temperature of 20 °C below the determined value and kept at this temperature for two hours.
  • another DSC run can be started, whereby the starting temperature must be at least 50 °C lower than the melting temperature assessed in the first DSC run.
  • the exact values of melting enthalpy, melting temperature, and maximum temperature of the curing reaction can be assessed in the second heating run. These values are displayed for the allyl functional polyesters in Table 1.
  • the weights per unsaturation (WPU) of the polymers can be determined by an adequate method known to someone skilled in the art, such as NMR or titration with iodine.
  • m refers to the mass of the one or more polyesters (A)
  • m polymer refers to the weighed portion of the one or more polymers (B).
  • the binding agent does not contain just one/more polyesters and just one/more polymers, then the sum of ( m polyesterA + m polymerB ) is to be understood as the sum of all binder components, i.e. the sum of all employed polymers.
  • the acid value (AV) is determined analogously to ONORM EN ISO 2114 with the difference that a mixture of 28 parts of acetone and 1 part of pyridine (% w/w) is used as a solvent.
  • a solvent for the partial acid value a mixture of 2 parts of pyridine and 1 part of methanol is used.
  • HV hydroxyl value
  • Polyesters (A) of the present invention were produced using the monomers according to Table 1 as follows:
  • polymer (B) is a polyester and produced in-house
  • all monomers and reactants are weighed in the reaction flask.
  • the flask is purged with nitrogen gas.
  • the mixture is heated up to 40°C
  • the MIBK is added using a dropping funnel.
  • the mixture is heated up to 225-242 °C.
  • the reaction water is collected and compared with the theoretical amount calculated from the resin formulation.
  • a vacuum of 500+/-50 mbar is applied. After 3.5 hours, the vacuum is raised to 300+/-50 mbar. The total vacuum time is around 4.5 hours.
  • the theoretical weight per unsaturation is provided, which was calculated as the ratio of the total mass (in g, unless stated differently) of the polyester/polymer obtained from the synthesis and the quantity of substance (in mol, unless stated differently) of the unsaturated monomer used for the production or the sum of the quantities of substance of the unsaturated monomers used for the production.
  • an extrusion is judged to be successful if it proceeds without any noticeable pre-reactions in the extruder.
  • Pre-reactions are recognized by a premature, at least partial polymerization of the powder coating. These pre-reactions take place when the temperature of the extrudate is too close to the temperature at which the half-life of the thermal initiator within the respective thermal initiation system is one minute. Experience has shown that this was the case at extrudate temperatures (measured at the exit of the extruder) starting from approx. T 1/2 -10°C on, in some cases from T 1/2 -20°C or T 1/2 -30°C on.
  • the processability was determined on the basis of any sticky residues during processing.
  • sticking is understood to be a phenomenon that needs additional mechanical impact for the formulation to be detached from the cooling unit.
  • the powder coating formulations according to Table 3 were electrostatically applied onto a medium density fibre board, reaching a film thickness of around 100 ⁇ 20 ⁇ m.
  • the powder coating formulations PC 1-PC 9 were thermally cured, using an IR oven.
  • the substrate temperature and the residence time in the oven are listed in Table 3.
  • the powder coating was molten in an IR heating zone for around six minutes, reaching a maximum temperature of the substrate of around 140 °C.
  • the curing was initiated with a mercury lamp, whereby the substrate temperature at the entry of the UV zone was around 120 °C.
  • the DSC measurements additionally employ a UV lamp (OMNICURE Series 2000), which was switched on at a temperature of 130 °C.
  • the resins have an amorphous character, exhibiting no detectable or only very low melting enthalpies. Particularly for resin 2, only a glass transition temperature and no melting temperature could be detected.
  • resins in accordance with the present invention are resins in accordance with the present invention.
  • resins 5-8 present preferred embodiments, prepared based on the preferred preparation procedure using a high amount of compounds supporting a crystalline structure, giving resins with a high degree of crystallinity.
  • PC 1 is a comparative example using PE 1, which has a very low amount of compounds supporting crystallinity. The processing was not possible, as the extrudate sticked to the cooling roller and to the cooling belt. No extrudate was obtained which could be used for milling, application and curing.
  • PC 7-9 present preferred embodiments, including a high amount of compounds supporting crystallinity in the polyester (A).
  • polymer (B) does not contain allyl functionalities.
  • PC 7-9 are optimized in terms of weight per unsaturations of polyester (A) and (B) as well as in terms of the amount of component B, leading to an optimized crosslinking density and thus to a superior resistance to cold liquids and performance in the Ledro test.
  • Table 2 Thermoplastic, amorphous, ethylenic unsaturated component (B) No.
EP18152573.4A 2018-01-19 2018-01-19 Thermoplastique Withdrawn EP3514206A1 (fr)

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EP18152573.4A EP3514206A1 (fr) 2018-01-19 2018-01-19 Thermoplastique
CN201980009299.8A CN111630115B (zh) 2018-01-19 2019-01-18 热塑性塑料
PCT/EP2019/051220 WO2019141800A1 (fr) 2018-01-19 2019-01-18 Thermoplastique
EP19700609.1A EP3740539B1 (fr) 2018-01-19 2019-01-18 Thermoplastique

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CN109476798A (zh) * 2016-07-21 2019-03-15 老虎涂料有限责任及两合公司 粉末涂层配方

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EP0309088B1 (fr) 1987-09-24 1995-11-15 Morton International, Inc. Poudre de revêtement dans le moule comprenant du 1,1'-di(t-butylperoxy)-3,3,5-triméthylcyclohexane comme initiateur.
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EP0844286A1 (fr) 1996-12-26 1998-05-27 Morton International, Inc. Revêtements en poudre durcissables thermiquement et par UV
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109476798A (zh) * 2016-07-21 2019-03-15 老虎涂料有限责任及两合公司 粉末涂层配方

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CN111630115B (zh) 2022-08-16
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CN111630115A (zh) 2020-09-04
WO2019141800A1 (fr) 2019-07-25

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